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Reorganización de la columna vertebral del carbono oxidativo en la biosíntesis de los risirilidos

Olga Tsypik¹, Roman Makitrynskyy¹, Britta Frensch²

¹Department of Pharmaceutical Biology and Biotechnology, Institute of Pharmaceutical Sciences, Albert-Ludwigs-Universität Freiburg, Stefan-Meier-Straße 19, 79104 Freiburg, Germany.

Journal of the American Chemical Society

|March 18, 2020

Resumen

Este estudio revela cómo las enzimas de Streptomyces bottropensis RslO5, RslO9 y RslO8 reorganizan los precursores de las policetidas. Estos pasos de adaptación redox generan moléculas complejas como rishirilides y lupinacidin A.

Área de la Ciencia:

La bioquímica
Biosíntesis de productos naturales
Enzimología

Sus antecedentes:

Las policetidas de tipo II exhiben una diversidad estructural significativa debido a las enzimas de adaptación.
Estudios previos de etiquetado C sugirieron reordenamientos complejos en la biosíntesis de rishirilida por Streptomyces bottropensis.

Objetivo del estudio:

Identificar los intermediarios biosintéticos clave en la formación de rishirilida y lupinacidina A.
Para dilucidar los intrincados pasos de adaptación redox involucrados en la biosíntesis de rishirilides A, B y D, y lupinacidina A.

Principales métodos:

Experimentos de eliminación de genes en el Streptomyces bottropensis.
Estudios enzimáticos in vitro de enzimas de adaptación aisladas.
Caracterización de los productos intermedios biosintéticos.

Principales resultados:

El RslO5 dependiente de la flavina abre reductivamente un anillo intermedio de epóxido.
La flavin monooxygenase RslO9 realiza un reordenamiento oxidativo de la columna vertebral del carbono a través de la oxidación de Baeyer-Villiger y la condensación de aldol.
La cetorreductaza RslO8 es esencial para la formación de rishirilidos A y B, mientras que RslO9 produce rishirilidos D y lupinacidina A.

Conclusiones:

Las reacciones de adaptación redox inusuales, incluida la oxidación de Baeyer-Villiger y la condensación de aldol, impulsan la diversificación estructural de los policetidos.
Las enzimas y vías identificadas proporcionan información sobre la biosíntesis de productos naturales complejos de policetida aromática.

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